CN1771274A - Resin composition for printed wiring board, prepreg, and laminate obtained with the same - Google Patents
Resin composition for printed wiring board, prepreg, and laminate obtained with the same Download PDFInfo
- Publication number
- CN1771274A CN1771274A CNA038265303A CN03826530A CN1771274A CN 1771274 A CN1771274 A CN 1771274A CN A038265303 A CNA038265303 A CN A038265303A CN 03826530 A CN03826530 A CN 03826530A CN 1771274 A CN1771274 A CN 1771274A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- weight
- parts
- printed wiring
- bisphenol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/226—Mixtures of di-epoxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2631—Coating or impregnation provides heat or fire protection
- Y10T442/2713—Halogen containing
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Reinforced Plastic Materials (AREA)
- Epoxy Resins (AREA)
- Laminated Bodies (AREA)
Abstract
Description
技术领域technical field
本发明涉及用于制造电气用层叠板等的印刷线路板用环氧树脂组成物、印刷线路板用半固化片及采用了半固化片的用于电子设备等的印刷线路板用层叠板、印刷线路板及多层印刷线路板。The present invention relates to an epoxy resin composition for printed wiring boards, a prepreg for printed wiring boards, a laminate for printed wiring boards used in electronic equipment, etc. using the prepreg, printed wiring boards, etc. layer printed circuit board.
背景技术Background technique
对印刷线路板用环氧树脂的固化剂而言，以往一直采用DICY(双氰胺)。然而近年来随着印刷线路板的高密度布线化，人们要求采用具有良好的长期绝缘可靠性(CAF)的材料及可对应于无铅焊锡的热分解温度较高的材料，对固化剂而言，开始采用具有上述良好特性的酚固化剂。然而，在采用这些固化剂来进行制造的场合下，存在着对玻璃基体材料的含浸性将变劣，且所制作出的半固化片的外观将恶化的问题。Conventionally, DICY (dicyandiamide) has been used as a curing agent for epoxy resins for printed wiring boards. However, in recent years, with the high-density wiring of printed circuit boards, it is required to use materials with good long-term insulation reliability (CAF) and materials with a high thermal decomposition temperature corresponding to lead-free solder. , began to use the phenolic curing agent with the above-mentioned good characteristics. However, when these curing agents are used for production, there is a problem that the impregnation property to the glass base material deteriorates, and the appearance of the produced prepreg deteriorates.
发明内容Contents of the invention
本发明鉴于上述问题，其目的在于：提供一种用于制作在通用FR-4印刷线路板中，热分解温度及烘箱耐热性等耐热性良好，并可实现阻燃性、玻璃化转移温度、成本等的平衡，且半固化片的外观良好的半固化片的印刷线路板用环氧树脂组成物和所制作的半固化片及采用了半固化片的层叠板。In view of the above problems, the present invention aims to provide a general-purpose FR-4 printed circuit board, which has good heat resistance such as thermal decomposition temperature and oven heat resistance, and can realize flame retardancy and glass transition. Epoxy resin composition for a printed wiring board of a prepreg having a balance of temperature, cost, etc., and having a good appearance of the prepreg, the produced prepreg, and a laminate using the prepreg.
对半固化片的外观改良而言，在特公平07-48586号公报及特公平07-68380号公报中，列举了在制造半固化片时，使四溴双酚A与双酚A型环氧树脂及清漆型环氧树脂进行反应，由此来改善环氧树脂组成物对基体材料的含浸性，从而改良半固体片的外观的示例等。本发明者对采用了通用环氧树脂组成物的印刷线路板用半固化片进行了各种探讨，发现了采用不同于上述的方法来确保印刷线路板用半固化片的阻燃性及玻璃化转移温度，从而有效改良印刷线路板用半固化片的外观的环氧树脂组成物，并由此而提出了本发明。For the improvement of the appearance of the prepreg, in the Japanese Patent Publication No. 07-48586 and the Publication No. 07-68380, it is listed that when the prepreg is manufactured, tetrabromobisphenol A and bisphenol A type epoxy resin and varnish type An example in which the epoxy resin reacts to improve the impregnation property of the base material with the epoxy resin composition, thereby improving the appearance of the semi-solid sheet, and the like. The inventors of the present invention conducted various studies on a prepreg for printed wiring boards using a general-purpose epoxy resin composition, and found that the flame retardancy and glass transition temperature of the prepreg for printed wiring boards were secured by a method different from the above, and thus The present invention is made of an epoxy resin composition effective in improving the appearance of a prepreg for printed wiring boards.
本发明的权利要求1的发明，是一种印刷线路板用环氧树脂组成物，由环氧树脂、酚清漆树脂、固化催化剂来组成，其特征在于：该环氧树脂由环氧树脂a及环氧树脂b来组成，环氧树脂a是一种溴化环氧树脂，该溴化环氧树脂通过使双酚A型环氧树脂与四溴双酚A进行反应并混合而得到，环氧树脂当量为350g/eq以上470g/eq以下，且GPC图面积比的n＝0成分为20％以上35％以下，环氧树脂b是一种以上的二官能环氧树脂，该二官能环氧树脂通过使双酚A、双酚F及四溴双酚A中的任意一种与表氯醇进行反应而得到，且GPC图的n＝0成分为60％以上，环氧树脂a与环氧树脂b的合计对该环氧树脂整体而言为80重量％以上100重量％以下，最好为93重量％以上100重量％以下，环氧树脂a对该环氧树脂整体而言为75重量％以上97重量％以下，而且溴含有率对该环氧树脂整体而言为18重量％以上30重量％以下。权利要求2的发明是一种印刷线路板用环氧树脂组成物，其特征在于：权利要求1所述的酚清漆树脂，是使由酚醛、甲酚及双酚A组成的任意一种与甲醛进行反应而得到的酚清漆树脂，而且是其二官能成分为15％以上30％以下的酚清漆树脂。权利要求3的发明是根据权利要求1或2所述的印刷线路板用环氧树脂组成物，其特征在于：配用无机充填剂而成。权利要求4的发明是根据权利要求3所述的印刷线路板用环氧树脂组成物，其特征在于：配用玻璃粉末及/或硅充填剂而成。权利要求5的发明是一种印刷线路板用半固化片，其特征在于：使权利要求1～4任意一项所述的印刷线路板用环氧树脂组成物及由有机溶剂组成的清漆含浸于玻璃布并干燥，从而达到B级化。权利要求6的发明是一种印刷线路板用层叠板、印刷线路板或多层印刷线路板，其特征在于：利用权利要求5所述的印刷线路板用半固化片来制作。The invention of claim 1 of the present invention is an epoxy resin composition for printed wiring board, which is composed of epoxy resin, phenol novolac resin, and curing catalyst, and is characterized in that: the epoxy resin is composed of epoxy resin a and Composed of epoxy resin b, epoxy resin a is a brominated epoxy resin, the brominated epoxy resin is obtained by reacting bisphenol A type epoxy resin with tetrabromobisphenol A and mixing, epoxy The resin equivalent is more than 350g/eq and less than 470g/eq, and the n=0 component of the GPC chart area ratio is more than 20% and less than 35%, the epoxy resin b is one or more difunctional epoxy resins, and the difunctional epoxy The resin is obtained by reacting any one of bisphenol A, bisphenol F and tetrabromobisphenol A with epichlorohydrin, and the n=0 component of the GPC chart is more than 60%, epoxy resin a and epoxy The total of resin b is 80% by weight or more and 100% by weight or less, preferably 93% by weight or more and 100% by weight or less of the epoxy resin as a whole, and epoxy resin a is 75% by weight or less of the epoxy resin as a whole The above is 97% by weight or less, and the bromine content is 18% by weight or more and 30% by weight or less for the epoxy resin as a whole. The invention of claim 2 is an epoxy resin composition for printed circuit boards, characterized in that the phenol novolak resin according to claim 1 is formed by mixing any one of phenol formaldehyde, cresol and bisphenol A with formaldehyde The phenol novolak resin obtained by carrying out the reaction is a phenol novolac resin whose difunctional component is 15% or more and 30% or less. The invention of claim 3 is the epoxy resin composition for printed wiring boards according to claim 1 or 2, characterized in that it contains an inorganic filler. The invention of claim 4 is the epoxy resin composition for printed wiring boards according to claim 3, characterized in that it is made by mixing glass powder and/or silicon filler. The invention according to claim 5 is a prepreg for printed wiring boards, characterized in that glass cloth is impregnated with the epoxy resin composition for printed wiring boards according to any one of claims 1 to 4 and a varnish composed of an organic solvent. And dry, so as to achieve B grade. The invention of claim 6 is a laminate for printed wiring boards, a printed wiring board, or a multilayer printed wiring board, characterized in that it is manufactured using the prepreg for printed wiring boards according to claim 5 .
具体实施方式Detailed ways
以下，说明本发明的实施方式。Embodiments of the present invention will be described below.
本发明中所用的环氧树脂，由环氧树脂a及环氧树脂b来组成，环氧树脂a是一种溴化环氧树脂，该溴化环氧树脂通过使双酚A型环氧树脂与四溴双酚A进行反应并混合而得到，环氧树脂当量为350g/eq以上470g/eq以下，且GPC图面积比的n＝0成分为20％以上35％以下，环氧树脂b是一种以上的二官能环氧树脂，该二官能环氧树脂通过使双酚A、双酚F及四溴双酚A中的任意一种与表氯醇进行反应而得到，且GPC图的n＝0成分为60％以上，环氧树脂a与环氧树脂b的合计对该环氧树脂整体而言为80重量％以上100重量％以下，最好为93重量％以上100重量％以下，环氧树脂a对该环氧树脂整体而言为75重量％以上97重量％以下，而且溴含有率对该环氧树脂整体而言为18重量％以上30重量％以下。The epoxy resin used among the present invention is made up of epoxy resin a and epoxy resin b, and epoxy resin a is a kind of brominated epoxy resin, and this brominated epoxy resin is passed through bisphenol A type epoxy resin It is obtained by reacting and mixing with tetrabromobisphenol A, the epoxy resin equivalent is 350 g/eq to 470 g/eq, and the n=0 component of the GPC chart area ratio is 20% to 35%, and the epoxy resin b is More than one difunctional epoxy resin obtained by reacting any one of bisphenol A, bisphenol F and tetrabromobisphenol A with epichlorohydrin, and the n of the GPC diagram =0 component is 60% or more, the total of epoxy resin a and epoxy resin b is 80% by weight or more and 100% by weight or less for the epoxy resin as a whole, preferably 93% by weight or more and 100% by weight or less. The oxygen resin a is 75% by weight or more and 97% by weight or less for the whole epoxy resin, and the bromine content is 18% by weight or more and 30% by weight or less for the whole epoxy resin.
本发明中所用的印刷线路板用环氧树脂组成物，有必要由上述环氧树脂、酚清漆树脂、固化催化剂来组成。The epoxy resin composition for printed wiring boards used in the present invention must consist of the above-mentioned epoxy resin, phenol novolac resin, and curing catalyst.
除了上述成分之外，在印刷线路板用环氧树脂组成物中，为了降低其固化物的热膨胀系数，最好配用无机充填剂。除了上述成分之外，在必要时也可以配用紫外线遮蔽剂及荧光发光剂等。In addition to the above components, an inorganic filler is preferably incorporated in the epoxy resin composition for printed wiring boards in order to reduce the thermal expansion coefficient of the cured product. In addition to the above-mentioned components, an ultraviolet shielding agent, a fluorescent luminescent agent, and the like may also be used if necessary.
对环氧树脂a而言，只要是一种使双酚A型环氧树脂与四溴双酚A进行反应并混合，环氧树脂当量为350g/eq以上470g/eq以下，且GPC图面积比的n＝0成分为20％以上35％以下的溴化环氧树脂即可，具体而言，可列举出长春人造公司生产的BEB530A80以及WUXI DICEPOXY有限公司生产的EPICLON1320-80A等。如果环氧树脂当量为350g/eq以下，则固化物便会固化。而如果环氧树脂当量为470g/eq以上，则固化物的玻璃化转移温度便会降低。在GPC图面积比的n＝0成分低于20％的场合下，半固化片的外观可能恶化。而如果超过35％，则树脂的流动性将可能加大。For epoxy resin a, as long as it is a kind of reaction and mixing of bisphenol A type epoxy resin and tetrabromobisphenol A, the equivalent weight of epoxy resin is more than 350g/eq and less than 470g/eq, and the GPC chart area ratio Brominated epoxy resins whose n=0 component is 20% or more and 35% or less may be used. Specifically, BEB530A80 produced by Changchun Manmade Co., Ltd. and EPICLON1320-80A produced by WUXI DICEPOXY Co., Ltd. can be mentioned. If the epoxy resin equivalent is 350 g/eq or less, the cured product will be cured. On the other hand, if the epoxy resin equivalent is more than 470 g/eq, the glass transition temperature of the cured product will decrease. When the n=0 component of the GPC chart area ratio is less than 20%, the appearance of the prepreg may deteriorate. And if it exceeds 35%, the fluidity of the resin may increase.
n＝0成分的GPC图面积比用下列方法来测定。The area ratio of the GPC chart of the n=0 component was determined by the following method.
(GPC测定：色谱分析法)(GPC measurement: chromatographic analysis method)
测定条件：溶剂：四氢呋喃(THF)、色谱柱：东洋索达有限公司制造G4000HXL+G3000HXL+G2000HXL+G2000HXL，流量：1ml/分，检测器：RI检测器。Measurement conditions: solvent: tetrahydrofuran (THF), column: G4000HXL+G3000HXL+G2000HXL+G2000HXL manufactured by Toyo Soda Co., Ltd., flow rate: 1 ml/min, detector: RI detector.
对环氧树脂b而言，只要是一种使双酚A、双酚F、四溴双酚A的任意一种与表氯醇进行反应，且GPC图的n＝0成分为60％以上的二官能环氧树脂即可，也可以二种并用。具体而言，可列举出大日本油墨化学工业公司生产：EPICLON153(溴化环氧树脂)及EPICLON840S(双酚A型环氧树脂)等。For epoxy resin b, as long as it is a kind of reaction of any one of bisphenol A, bisphenol F, and tetrabromobisphenol A with epichlorohydrin, and the n=0 component of the GPC chart is 60% or more A difunctional epoxy resin may be used, or both may be used in combination. Specifically, EPICLON 153 (brominated epoxy resin) and EPICLON 840S (bisphenol A type epoxy resin) manufactured by Dainippon Ink Chemical Co., Ltd., etc. are mentioned.
环氧树脂a与环氧树脂b的合计对环氧树脂整体而言为80重量％以上100重量％以下，最好为93重量％以上100重量％以下，环氧树脂a为75重量％以上97重量％以下，通过如此配合，可满足适合固化物的玻璃化转移温度及半固化片的外观。此外，对环氧树脂整体而言，使溴含浸量处于18重量％以上30重量％以下的范围，由此可确保固化物场合下的阻燃性(UL标准中的V-O)The total of epoxy resin a and epoxy resin b is 80% by weight or more and 100% by weight or less, preferably 93% by weight or more and 100% by weight or less for the epoxy resin as a whole, and epoxy resin a is 75% by weight or more and 97% by weight. % by weight or less, by blending in this way, the glass transition temperature of the cured product and the appearance of the prepreg can be satisfied. In addition, the flame retardancy (V-O in UL standard) of the cured product can be ensured by setting the bromine impregnation amount in the range of 18% by weight to 30% by weight with respect to the entire epoxy resin.
在本发明中，除了上述环氧树脂a、b之外，也可以采用其它环氧树脂。尽管没有特别限定，但仍要举出：甲酚清漆型环氧树脂等清漆型环氧树脂、双环戊二烯型环氧树脂、四甲基双酚型二官能环氧树脂等双酚型环氧树脂、三官能型环氧树脂及四官能型环氧树脂等多官能型环氧树脂、对苯二酚型环氧树脂等。In the present invention, other epoxy resins may be used in addition to the above-mentioned epoxy resins a and b. Although not particularly limited, there may be mentioned: varnish-type epoxy resins such as cresol novolak-type epoxy resins, bisphenol-type epoxy resins such as dicyclopentadiene-type epoxy resins, and tetramethylbisphenol-type difunctional epoxy resins. Multifunctional epoxy resins such as oxygen resins, trifunctional epoxy resins and tetrafunctional epoxy resins, hydroquinone epoxy resins, etc.
在本发明中，尽管对用作固化剂的酚清漆树脂没有特别限定，但最好采用使酚醛及甲酚A的任意一种与甲醛进行反应后而得到的酚清漆树脂，如果是一种其二官能成分为15％以上30％以下的酚清漆树脂，则可提高利用它制作出的半固化片的成型性。此外，如果环氧基与酚醛性羟基的当量比达到1∶1.2～1∶0.7，则固化物的玻璃化转移温度与剥离强度等性能的平衡性将更好。In the present invention, although the novolac resin used as a curing agent is not particularly limited, it is preferable to use a novolak resin obtained by reacting any one of phenolic formaldehyde and cresol A with formaldehyde. A phenol novolac resin with a difunctional component of 15% to 30% can improve the moldability of the prepreg produced by it. In addition, if the equivalent ratio of epoxy groups to phenolic hydroxyl groups reaches 1:1.2 to 1:0.7, the balance between the glass transition temperature and peel strength of the cured product will be better.
对本发明的有机溶剂而言，最好采用丁酮与环己酮等酮类及甲氧基丙醇等乙二醇乙醚类。For the organic solvent of the present invention, ketones such as butanone and cyclohexanone, and glycol ethers such as methoxypropanol are preferably used.
对本发明的固化催化剂而言，尽管没有特别限定，但可列举出2-甲基咪唑、2-乙基-4甲基咪唑、2-酚咪唑、1-氰乙基-2-乙基-4-甲基咪唑等咪唑类；苄基二甲基胺等三级胺类；三丁基膦、三苯基膦等有机膦类；咪唑硅烷类，它们可以单独使用，也可以二种以上并用。For the curing catalyst of the present invention, although not particularly limited, 2-methylimidazole, 2-ethyl-4 methylimidazole, 2-phenolimidazole, 1-cyanoethyl-2-ethyl-4 - imidazoles such as methylimidazole; tertiary amines such as benzyldimethylamine; organic phosphines such as tributylphosphine and triphenylphosphine; and imidazole silanes. These may be used alone or in combination of two or more.
对本发明的无机充填剂而言，尽管没有特别限定，但可采用比如氢氧化铝、氢氧化镁、滑石、烧结滑石、高岭土、烧结高岭土、白陶土、烧结白陶土、天然硅石、合成硅石、玻璃粉等，最好采用硅石及玻璃粉。对这些充填剂而言，进行硅烷耦合剂等表面处理的一方的树脂与充填剂的界面强度可增大。无机充填剂的平均粒径最好为0.3μm以上30μm以下。当平均粒径超过30μm后，在旨在清除清漆中的异物的过滤工序中，可能会发生堵塞。此外，无机充填剂的添加量对固体树脂100重量份而言最好为5重量份以上7重量份以下。而且，如果采用玻璃粉及硅石充填剂，则可减少固化物的玻璃化转移温度的下降，并可降低固化物的热膨胀系数。As the inorganic filler of the present invention, although not particularly limited, for example, aluminum hydroxide, magnesium hydroxide, talc, sintered talc, kaolin, sintered kaolin, kaolin, sintered kaolin, natural silica, synthetic silica, glass Powder, etc., preferably silica and glass powder. For these fillers, the interface strength between the resin and the filler can be increased by surface treatment such as a silane coupling agent. The average particle diameter of the inorganic filler is preferably not less than 0.3 μm and not more than 30 μm. When the average particle size exceeds 30 μm, clogging may occur in the filtration process for removing foreign matter in varnish. In addition, the addition amount of the inorganic filler is preferably 5 parts by weight or more and 7 parts by weight or less with respect to 100 parts by weight of the solid resin. Moreover, if glass powder and silica filler are used, the glass transition temperature drop of the cured product can be reduced, and the thermal expansion coefficient of the cured product can be reduced.
以下说明半固化片的制造。The manufacture of the prepreg will be described below.
在上述环氧树脂中，配用固化剂和固化催化剂及有机溶剂，利用搅拌机或纳米混合机对它们进行均匀混合，由此来调制印刷线路板用环氧树脂组成物。A curing agent, a curing catalyst, and an organic solvent are mixed with the above-mentioned epoxy resin, and these are uniformly mixed with a mixer or a nano mixer to prepare an epoxy resin composition for a printed wiring board.
使所得到的印刷线路板用环氧树脂组成物含浸于基体材料玻璃布，并在干燥机中(120-180℃)进行干燥，其固化时间为60秒以上180秒以下，由此可制造出半固化状态(B级)的印刷线路板用半固化片。The obtained epoxy resin composition for printed wiring boards is impregnated into the base material glass cloth, and dried in a drier (120-180°C), and the curing time is 60 seconds to 180 seconds, thereby producing Prepreg for printed wiring boards in a semi-cured state (B grade).
接下来，将上述制作的半固化片按所需个数来重叠，并将其置于140～200℃、0.94～4.9MPa的条件下进行加热加压，从而层叠成型，由此可制造出印刷线路板用层叠板。此时，在按所需个数重叠的印刷线路板用半固化片的单侧或双侧重叠金属箔，从而层叠成型，由此可制造出用于印刷线路板加工的覆有金属箔的层叠板。这里，对金属箔而言，可采用铜箔、银箔、铝箔、不锈钢箔等。Next, stack the prepregs produced above according to the required number, and heat and press them under the conditions of 140-200°C and 0.94-4.9MPa, so as to be laminated and formed, and a printed circuit board can be manufactured. Use laminated boards. At this time, a desired number of prepreg sheets for printed wiring boards are stacked with metal foil on one or both sides to form a laminate, thereby producing a metal foil-clad laminate for printed wiring board processing. Here, as the metal foil, copper foil, silver foil, aluminum foil, stainless steel foil, etc. can be used.
这样，在上述制造出的印刷线路板用层叠板的外侧形成电路(形成图形)，由此可制造出印刷线路板。具体而言，对覆有金属箔的层叠板外侧的金属箔，通过实施递减法等来形成电路，即使外层不是金属箔，也可以通过递增法等来形成电路，从而可完成印刷线路板。In this way, a printed wiring board can be manufactured by forming a circuit (patterning) on the outer side of the printed wiring board laminate manufactured above. Specifically, the metal foil on the outer side of the metal foil-clad laminate is formed by a subtractive method or the like to form a circuit. Even if the outer layer is not a metal foil, the circuit can be formed by an incremental method or the like to complete a printed wiring board.
利用印刷线路板用半固化片、印刷线路板用层叠板及印刷线路板中的任意一个来层叠成型，由此可制造多层印刷线路板。具体而言，按上述来形成电路并将制成的印刷线路板用作内层用基板，在该内层用基板的单侧或两侧重叠所需个数的印刷线路板用半固化片，且在其外侧配置金属箔，向外侧配置金属箔的金属箔侧，对其加热加压，从而形成层叠，由此可制造出多层印刷线路板。此时，成型温度最好设定为150～180℃。A multilayer printed wiring board can be produced by laminating and molding any one of a prepreg for a printed wiring board, a laminate for a printed wiring board, and a printed wiring board. Specifically, a circuit is formed as described above and the resulting printed wiring board is used as a substrate for an inner layer, a required number of prepregs for a printed wiring board are stacked on one side or both sides of the substrate for an inner layer, and A metal foil is placed on the outside, and the metal foil side of the metal foil is placed on the outside, and this is heated and pressed to form a laminate, whereby a multilayer printed wiring board can be manufactured. At this time, the molding temperature is preferably set at 150 to 180°C.
根据本发明，最终得到的印刷线路板等，具有良好的阻燃性、成本、玻璃化转移温度及高耐热性的平衡。According to the present invention, the finally obtained printed wiring board and the like have a good balance of flame retardancy, cost, glass transition temperature and high heat resistance.
以下利用实施例来具体说明本发明。The present invention will be specifically described below using examples.
首先，依次表示所用的环氧树脂(环氧树脂a、环氧树脂b及其它环氧树脂)、固化剂、无机充填剂、固化催化剂及有机溶剂是。First, the epoxy resin (epoxy resin a, epoxy resin b and other epoxy resins), curing agent, inorganic filler, curing catalyst and organic solvent used are shown in order.
对环氧树脂而言，采用以下的材料。For the epoxy resin, the following materials were used.
环氧树脂a：是一种溴化环氧树脂，其中，使双酚A型环氧树脂与四溴双酚A进行反应并混合，环氧树脂当量为350g/eq以上470g/eq以下，且GPC图面积比的n＝0成分为20％以上35％以下，对这种树脂而言，采用了以下材料：Epoxy resin a: a brominated epoxy resin in which bisphenol A type epoxy resin and tetrabromobisphenol A are reacted and mixed, and the epoxy resin equivalent is 350 g/eq or more and 470 g/eq or less, and The n=0 component of the area ratio of the GPC chart is 20% to 35%. For this resin, the following materials are used:
环氧树脂1：大宇化学公司制造DER530A80Epoxy resin 1: DER530A80 manufactured by Daewoo Chemical Co., Ltd.
环氧树脂当量：427g/eq，n＝0成分：28％Epoxy equivalent weight: 427g/eq, n=0 Composition: 28%
环氧树脂2：WUXI DIC EPOXY有限公司制造Epiclon1320A80Epoxy resin 2: Epiclon 1320A80 manufactured by WUXI DIC EPOXY Co., Ltd.
环氧树脂当量：430g/eq，n＝0成分：26％Epoxy resin equivalent: 430g/eq, n=0 Composition: 26%
环氧树脂3：长春人造公司制造BEB530A80Epoxy resin 3: BEB530A80 made by Changchun Artificial Co., Ltd.
环氧树脂当量：438g/eq，n＝0成分：27％Epoxy resin equivalent weight: 438g/eq, n=0 Composition: 27%
环氧树脂4：格利斯公司制造GER454A80Epoxy resin 4: GER454A80 made by Gliss Corporation
环氧树脂当量：435g/eq，n＝0成分：27％Epoxy equivalent weight: 435g/eq, n=0 Composition: 27%
环氧树脂5：大宇化学公司制造DER539A80Epoxy resin 5: DER539A80 manufactured by Daewoo Chemical Co., Ltd.
环氧树脂当量：450g/eq，n＝0成分：21％Epoxy equivalent weight: 450g/eq, n=0 Composition: 21%
环氧树脂6：大日本化学公司制造Epiclon1120-80MEpoxy resin 6: Epiclon 1120-80M manufactured by Dainippon Chemical Co., Ltd.
环氧树脂当量：500g/eq，n＝0成分：17％(比较用)Epoxy resin equivalent: 500g/eq, n=0 Composition: 17% (for comparison)
环氧树脂b：是二官能环氧树脂，通过使双酚A、双酚F及四溴双酚A中的任意一种与表氯醇进行反应而得到，对这种树脂而言，采用了以下材料。Epoxy resin b: It is a difunctional epoxy resin obtained by reacting any one of bisphenol A, bisphenol F and tetrabromobisphenol A with epichlorohydrin. For this resin, the The following materials.
环氧树脂7：大日本油墨化学工业公司制造Epiclon153Epoxy resin 7: Epiclon 153 manufactured by Dainippon Ink Chemical Industry Co., Ltd.
溴化环氧树脂环氧树脂当量：400g/eq，n＝0成分：68％Brominated Epoxy Resin Epoxy Resin Equivalent: 400g/eq, n=0 Composition: 68%
环氧树脂8：大日本油墨化学工业公司制造Epiclon840SEpoxy resin 8: Epiclon 840S manufactured by Dainippon Ink Chemical Industry Co., Ltd.
双酚A型环氧树脂环氧树脂当量：190g/eq，n＝0成分：86％Bisphenol A type epoxy resin Epoxy equivalent weight: 190g/eq, n=0 Composition: 86%
环氧树脂9：大日本油墨化学工业公司制造Epiclon830SEpoxy resin 9: Epiclon 830S manufactured by Dainippon Ink Chemical Industry Co., Ltd.
双酚F型环氧树脂环氧树脂当量：170g/eq，n＝0成分：78％Bisphenol F type epoxy resin Epoxy equivalent: 170g/eq, n=0 Composition: 78%
对其它环氧树脂而言，采用了下列材料。For other epoxy resins, the following materials were used.
环氧树脂10：壳牌化学公司制造EPON Resin 1031Epoxy resin 10: EPON Resin 1031 manufactured by Shell Chemical Company
四官能型环氧树脂环氧树脂当量：212g/eqFour-functional epoxy resin Epoxy resin equivalent: 212g/eq
环氧树脂11：东都化成制造TDCN-704Epoxy resin 11: TDCN-704 manufactured by Tohto Kasei
甲酚清漆型环氧树脂环氧树脂当量：220g/eqCresyl varnish type epoxy resin Epoxy resin equivalent: 220g/eq
对固化剂而言，采用了以下材料。For the curing agent, the following materials were used.
固化剂1：日本环氧树脂公司制造YLH129B70Curing agent 1: YLH129B70 manufactured by Japan Epoxy Resin Co., Ltd.
双酚A型清漆二官能成分：17～19％羟基当量：118g/eqBifunctional component of bisphenol A type varnish: 17-19% Hydroxyl equivalent: 118g/eq
固化剂2：大日本油墨化学工业公司制造TD 2093Curing agent 2: TD 2093 manufactured by Dainippon Ink Chemical Industry Co., Ltd.
酚清漆二官能成分：7～8％羟基当量：105g/qDifunctional component of phenol novolac: 7-8% Hydroxyl equivalent: 105g/q
固化剂3：大日本油墨化学工业公司制造VH-4170Curing agent 3: VH-4170 manufactured by Dainippon Ink Chemical Industry Co., Ltd.
双酚A型清漆二官能成分：25％羟基当量：118g/eqBisphenol A type varnish difunctional component: 25% Hydroxyl equivalent: 118g/eq
固化剂4：双氰胺试剂品 理论活性氢当量：21g/eqCuring agent 4: dicyandiamide reagent Theoretical active hydrogen equivalent: 21g/eq
对固化催化剂而言，采用了以下材料。For the curing catalyst, the following materials were used.
催化剂1：四国化成公司制造：2-乙基-4-甲基咪唑Catalyst 1: Manufactured by Shikoku Chemicals Co., Ltd.: 2-Ethyl-4-methylimidazole
对无机充填剂而言，采用了下列材料。For the inorganic filler, the following materials were used.
无机充填剂1：E玻璃粉SS公司制造Inorganic filler 1: E glass powder made by SS company
REV1纤维直径13μm，纤维长度35μmREV1 fiber diameter 13μm, fiber length 35μm
无机充填剂2：硅石龙森公司制造MSR-04球状硅石平均粒径4μmInorganic filler 2: Silica MSR-04 spherical silica manufactured by Longsen Co., Ltd. Average particle size 4 μm
无机充填剂3：滑石富士滑石公司制造烧结PKP-81平均粒径13μmInorganic filler 3: Talc Fuji Talc Co., Ltd. Sintered PKP-81 Average particle size 13 μm
对有机溶剂而言，采用了下列材料。For the organic solvent, the following materials were used.
有机溶剂1：丁酮Organic solvent 1: Butanone
有机溶剂2：甲氧基丙醇Organic solvent 2: Methoxypropanol
有机溶剂3：环己酮Organic solvent 3: cyclohexanone
有机溶剂4：二甲替甲酰胺Organic solvent 4: Dimethylformamide
(实施例1)(Example 1)
准备环氧树脂1(112.5重量份)及环氧树脂7(10重量份)、固化剂1(39.5重量份)、有机溶剂2(18.6重量份)，并搅拌90分钟，并配用催化剂1(0.13重量份)，并搅拌30分钟，由此得到清漆。Prepare epoxy resin 1 (112.5 parts by weight) and epoxy resin 7 (10 parts by weight), curing agent 1 (39.5 parts by weight), organic solvent 2 (18.6 parts by weight), and stirred for 90 minutes, and equipped with catalyst 1 ( 0.13 parts by weight) and stirred for 30 minutes to obtain a varnish.
(实施例2)(Example 2)
准备环氧树脂2(118.8重量份)和环氧树脂8(5重量份)及环氧树脂10(3重量份)、固化剂1(44.0重量份)、有机溶剂2(35重量份)，并搅拌90分钟，并配用催化剂1(0.13重量份)，并搅拌30分钟，由此得到清漆。Prepare epoxy resin 2 (118.8 parts by weight) and epoxy resin 8 (5 parts by weight) and epoxy resin 10 (3 parts by weight), curing agent 1 (44.0 parts by weight), organic solvent 2 (35 parts by weight), and After stirring for 90 minutes, catalyst 1 (0.13 parts by weight) was added and stirred for 30 minutes to obtain a varnish.
(实施例3)(Example 3)
准备环氧树脂3(118.8重量份)和环氧树脂9(5重量份)及环氧树脂10(5重量份)、固化剂2(34.2重量份)、有机溶剂1(8重量份)和有机溶剂2(17.6重量份)及有机溶剂3(25.6重量份)，并搅拌90分钟，并配用催化剂1(0.13重量份)，并搅拌30分钟，由此得到清漆。Prepare epoxy resin 3 (118.8 parts by weight) and epoxy resin 9 (5 parts by weight) and epoxy resin 10 (5 parts by weight), curing agent 2 (34.2 parts by weight), organic solvent 1 (8 parts by weight) and organic Solvent 2 (17.6 parts by weight) and organic solvent 3 (25.6 parts by weight) were stirred for 90 minutes, and catalyst 1 (0.13 parts by weight) was added and stirred for 30 minutes to obtain a varnish.
(实施例4)(Example 4)
准备环氧树脂4(118.8重量份)和环氧树脂8(5重量份)、固化剂3(29.2重量份)、有机溶剂2(22.9重量份)，并搅拌90分钟，并配用催化剂1(0.13重量份)，并搅拌30分钟，由此得到清漆。Prepare epoxy resin 4 (118.8 parts by weight) and epoxy resin 8 (5 parts by weight), curing agent 3 (29.2 parts by weight), organic solvent 2 (22.9 parts by weight), and stir 90 minutes, and be equipped with catalyst 1 ( 0.13 parts by weight) and stirred for 30 minutes to obtain a varnish.
(实施例5)(Example 5)
准备环氧树脂5(93.8重量份)和环氧树脂7(25重量份)、固化剂1(38.6重量份)、有机溶剂1(8重量份)和有机溶剂2(19重量份)及有机溶剂3(19重量份)，并搅拌90分钟，并配用催化剂1(0.13重量份)，并搅拌30分钟，然后搅拌无机充填剂1(每100重量份固体树脂为15重量份)，同时进行添加，在搅拌90分钟后，利用纳米搅拌机来进一步分散清漆中的无机充填剂，由此得到清漆。Prepare epoxy resin 5 (93.8 parts by weight) and epoxy resin 7 (25 parts by weight), curing agent 1 (38.6 parts by weight), organic solvent 1 (8 parts by weight) and organic solvent 2 (19 parts by weight) and organic solvent 3 (19 parts by weight), and stirred for 90 minutes, and equipped with catalyst 1 (0.13 parts by weight), and stirred for 30 minutes, then stirred inorganic filler 1 (15 parts by weight per 100 parts by weight of solid resin), while adding , after stirring for 90 minutes, a nano mixer was used to further disperse the inorganic filler in the varnish, thereby obtaining the varnish.
(实施例6)(Example 6)
准备环氧树脂2(112.5重量份)和环氧树脂7(10重量份)、固化剂1(39.5重量份)、有机溶剂2(25重量份)和有机溶剂3(25重量份)，并搅拌90分钟，并配用催化剂1(0.13重量份)，并搅拌30分钟，然后搅拌无机充填剂2(每100重量份固体树脂为15重量份)，同时进行添加，在搅拌90分钟后，利用纳米搅拌机来进一步分散清漆中的无机充填剂，由此得到清漆。Prepare epoxy resin 2 (112.5 parts by weight) and epoxy resin 7 (10 parts by weight), curing agent 1 (39.5 parts by weight), organic solvent 2 (25 parts by weight) and organic solvent 3 (25 parts by weight), and stir 90 minutes, and equipped with catalyst 1 (0.13 parts by weight), and stirred for 30 minutes, then stirred inorganic filler 2 (per 100 parts by weight of solid resin is 15 parts by weight), while adding, after stirring for 90 minutes, using nano The mixer is used to further disperse the inorganic filler in the varnish, thereby obtaining the varnish.
(实施例7)(Example 7)
除了对无机充填剂而言，将无机充填剂1置换为无机充填剂3之外，与实施例5的做法相同。Except for the inorganic filler, the inorganic filler 1 was replaced with the inorganic filler 3, the procedure was the same as that of Example 5.
(比较例1)(comparative example 1)
准备环氧树脂3(106重量份)和环氧树脂11(15重量份)、固化剂1(44.8重量份)、有机溶剂1(26重量份)和有机溶剂2(10重量份)，并搅拌90分钟，并配用催化剂1(0.13重量份)，并搅拌30分钟，由此得到清漆。Prepare epoxy resin 3 (106 parts by weight) and epoxy resin 11 (15 parts by weight), curing agent 1 (44.8 parts by weight), organic solvent 1 (26 parts by weight) and organic solvent 2 (10 parts by weight), and stir After 90 minutes, catalyst 1 (0.13 parts by weight) was added and stirred for 30 minutes to obtain a varnish.
(比较例2)(comparative example 2)
准备环氧树脂6(118.8重量份)和环氧树脂8(5重量份)、固化剂1(41.7重量份)、有机溶剂2(33.3重量份)，并搅拌90分钟，并配用催化剂1(0.13重量份)，并搅拌30分钟，由此得到清漆。Prepare epoxy resin 6 (118.8 parts by weight) and epoxy resin 8 (5 parts by weight), curing agent 1 (41.7 parts by weight), organic solvent 2 (33.3 parts by weight), and stir 90 minutes, and be equipped with catalyst 1 ( 0.13 parts by weight) and stirred for 30 minutes to obtain a varnish.
(比较例3)(comparative example 3)
准备环氧树脂6(125重量份)、固化剂2(21重量份)、有机溶剂1(30重量份)及有机溶剂2(10重量份)，并搅拌90分钟，并配用催化剂1(0.13重量份)，并搅拌30分钟，由此得到清漆。Prepare epoxy resin 6 (125 parts by weight), curing agent 2 (21 parts by weight), organic solvent 1 (30 parts by weight) and organic solvent 2 (10 parts by weight), and stir for 90 minutes, and be equipped with catalyst 1 (0.13 parts by weight), and stirred for 30 minutes, thus obtaining a varnish.
(比较例4)(comparative example 4)
准备环氧树脂6(106重量份)及环氧树脂11(15重量份)、固化剂4(2.5重量份)、有机溶剂1(13重量份)和有机溶剂2(10.6重量份)及有机溶剂3(23.6重量份)，并搅拌90分钟，并配用催化剂1(0.05重量份)，并搅拌30分钟，由此得到清漆。Prepare epoxy resin 6 (106 parts by weight) and epoxy resin 11 (15 parts by weight), curing agent 4 (2.5 parts by weight), organic solvent 1 (13 parts by weight) and organic solvent 2 (10.6 parts by weight) and organic solvent 3 (23.6 parts by weight) and stirred for 90 minutes, and catalyst 1 (0.05 parts by weight) was added and stirred for 30 minutes to obtain a varnish.
<印刷线路板半固化片的制造方法><Manufacturing method of printed wiring board prepreg>
使实施例1～7及比较例1～4的印刷线路板用树脂组成物清漆分别含浸于厚度为0.2mm的玻璃布(日东纺公司制造「WEA7628」)，在干燥机中(120～180℃)进行干燥，半固化片的固化时间为60秒以上180秒以下，以使树脂量达到40重量％或46重量％，从而制成半固化状态(B级)的印刷线路板用半固化片。The resin composition varnishes for printed wiring boards of Examples 1 to 7 and Comparative Examples 1 to 4 were respectively impregnated into glass cloth with a thickness of 0.2 mm ("WEA7628" manufactured by Nittobo Co., Ltd.), and dried in a dryer (120 to 180 ℃) for drying, the curing time of the prepreg is not less than 60 seconds and not more than 180 seconds, so that the resin content reaches 40% by weight or 46% by weight, thereby making a prepreg for printed wiring boards in a semi-cured state (Class B).
<覆铜层叠板的制造方法><Manufacturing method of copper clad laminate>
在4个或8个所得到的40重量％印刷线路板用半固化片的两面放置铜箔，在140～180℃及0.98～3.9MPa的条件下，用压力机对其加热加压，从而层叠成型，由此制成板厚为0.8mm及1.6mm的覆铜层叠板。Place copper foil on both sides of 4 or 8 obtained 40% by weight prepregs for printed wiring boards, and heat and press them with a press under the conditions of 140-180°C and 0.98-3.9MPa to form laminates. In this way, copper-clad laminates having thicknesses of 0.8 mm and 1.6 mm were produced.
这里，层叠成型时的加热时间设定为：印刷线路板用半固化片整体温度达到160℃以上所需的时间至少为60分钟以上。对铜箔而言，采用古河箔片公司生产的「GT」产品(厚度为18μm)。Here, the heating time during lamination molding is set such that the time required for the temperature of the entire prepreg for a printed wiring board to reach 160° C. or higher is at least 60 minutes or longer. For the copper foil, the "GT" product (thickness 18 μm) produced by Furukawa Foil Co., Ltd. was used.
对上述得到的印刷线路板用半固化片及覆铜层叠板而言，进行了下述物理性评估。其结果如表1所示。The following physical property evaluation was performed about the prepreg for printed wiring boards obtained above, and a copper-clad laminated board. The results are shown in Table 1.
(半固化片(PP)的外观)(Appearance of prepreg (PP))
用肉眼观察了利用上述印刷线路板用半固化片的制造方法得到的树脂量46％产品的外观。The appearance of the product having a resin content of 46% obtained by the above-mentioned method for producing a prepreg for a printed wiring board was visually observed.
(玻璃化转移温度)(glass transition temperature)
利用蚀刻法来除去上述得到的覆铜层叠片的铜箔，并按照IPC-TM-650 2.4.25标准，用DSC法进行了测定。The copper foil of the copper-clad laminate obtained above was removed by etching, and measured by the DSC method in accordance with IPC-TM-650 2.4.25.
将玻璃化转移温度125℃以上的产品标为『○』。Products with a glass transition temperature of 125°C or higher are marked as "○".
(阻燃性)(flame retardant)
在阻燃性的评估中，利用蚀刻法，从板厚为0.8mm的覆铜层叠板除去表面铜箔，将其切成：长度为125mm，宽度为13mm，并利用UL法(UL94)，进行了垂直燃烧试验。In the evaluation of flame retardancy, the surface copper foil was removed from a copper-clad laminate with a plate thickness of 0.8mm by etching, and it was cut into pieces: length 125mm, width 13mm, and UL method (UL94). vertical burning test.
(成型性)(formability)
利用上述的印刷线路板用半固化片制造方法，来制成固化时间不同的半固化片(树脂量为40％)，按照上述记载的印刷线路板用层叠板的制造方法，使这些半固化片成型，从而得到了覆铜层叠板。此后，利用蚀刻来除去铜箔，并观察了砂眼及粗疵。在固化时间较长的情况下，没有砂眼及粗疵，成型性良好，将在固化时间120秒的范围内质量良好的产品判定为『○』，将在固化时间100秒的范围内质量良好的产品判定为『△』。Using the above-mentioned method for producing a prepreg for a printed wiring board, prepregs (resin content: 40%) having different curing times were produced, and these prepregs were molded according to the method for producing a laminate for a printed wiring board described above, thereby obtaining a laminate. copper laminate. Thereafter, the copper foil was removed by etching, and blisters and roughness were observed. In the case of a long curing time, there are no blisters and rough defects, and the moldability is good. The product with good quality within the curing time of 120 seconds is judged as "○", and the product with good quality within the curing time of 100 seconds is judged as "○". The product was judged as "△".
(固化时间测定)(Measurement of curing time)
将上述制作出的半固化片揉碎，从而成为粉末，(从60目过滤器中通过，从而除去玻璃纤维等异物)，并按照JIS C652 1 5.7标准进行了测定。The prepreg produced above was pulverized into a powder (passed through a 60-mesh filter to remove foreign matter such as glass fibers), and measured in accordance with JIS C652 1 5.7.
(热膨胀系数)(Thermal expansion coefficient)
利用蚀刻法来除去上述得到的1.6mm覆铜层叠板的铜箔，并按照IPC-TM-650 2.4.24标准，利用TMA法进行了测定。The copper foil of the 1.6 mm copper-clad laminate obtained above was removed by etching, and measured by the TMA method in accordance with IPC-TM-650 2.4.24.
(烘箱耐热性)(Oven heat resistance)
按照JIS-C6481标准，对上述得到的覆铜层叠板进行了评估。The copper-clad laminated board obtained above was evaluated according to JIS-C6481 standard.
(热分解温度)(Thermal decomposition temperature)
利用蚀刻法来除去上述得到的覆铜层叠板的铜箔，并利用TG/DTA，在10℃温升条件下进行了测定。将热分解温度设为：使重量减少5％。The copper foil of the copper-clad laminated board obtained above was removed by etching, and it measured by TG/DTA under 10 degreeC temperature rise conditions. The thermal decomposition temperature was set to reduce the weight by 5%.
(表1)(Table 1)
对应于环氧树脂A请求项←————————————————————————————————————Corresponding to the epoxy resin A request item ←——————————————————————————————————————
对应于环氧树脂B请求项←————————————————————————————————————
环氧树脂A—————————————————————————————————————————————对应于请求项Epoxy resin A———————————————————————————————————————————————————————————————————— on request
环氧树脂B—————————————————————————————————————————————不用
环氧树脂A非对应 非对应Epoxy resin A non-corresponding non-corresponding
环氧树脂B对应于请求项 不用 DICY固化
◆双酚A型环氧树脂与四溴双酚A进行反应后生成的溴化环氧树脂◆Brominated epoxy resin produced by reacting bisphenol A epoxy resin with tetrabromobisphenol A
环氧树脂1：大宇化学公司制造DER530A80环氧树脂当量：427g/eq，n＝0成分：28％Epoxy resin 1: DER530A80 manufactured by Daewoo Chemical Co., Ltd. Epoxy resin equivalent: 427g/eq, n=0 Composition: 28%
环氧树脂2：WUXI DIC EPOXY公司制造Epiclon1320A80环氧树脂当量：430g/eq，n＝0成分：26％Epoxy resin 2: Epiclon 1320A80 made by WUXI DIC EPOXY company Epoxy resin equivalent: 430g/eq, n=0 Composition: 26%
环氧树脂3：长春人造公司制造BEB530A80环氧树脂当量：438g/eq，n＝0成分：27％Epoxy resin 3: BEB530A80 manufactured by Changchun Manmade Co., Ltd. Epoxy resin equivalent: 438g/eq, n=0 Composition: 27%
环氧树脂4：格利斯公司制造GER454A80环氧树脂当量：435g/eq，n＝0成分：27％Epoxy resin 4: GER454A80 manufactured by Gliss Corporation Epoxy resin equivalent: 435g/eq, n=0 Component: 27%
环氧树脂5：大宇化学公司制造DER539A80环氧树脂当量：450g/eq，n＝0成分：21％Epoxy resin 5: DER539A80 manufactured by Daewoo Chemical Co., Ltd. Epoxy resin equivalent: 450g/eq, n=0 Composition: 21%
环氧树脂6：大日本化学公司制造Epiclon1120-80M环氧树脂当量：500g/eq，n＝0成分：17％Epoxy resin 6: Epiclon 1120-80M manufactured by Dainippon Chemical Co., Ltd. Epoxy resin equivalent: 500g/eq, n=0 Component: 17%
◆二官能环氧树脂，通过使双酚A、双酚F及四溴双酚A中的任意一种与表氯醇进行反应而得到◆Difunctional epoxy resin obtained by reacting any one of bisphenol A, bisphenol F and tetrabromobisphenol A with epichlorohydrin
环氧树脂7：大日本油墨化学工业公司制造Epiclon153溴化环氧树脂环氧树脂当量：400g/eq，n＝0成分：68％Epoxy resin 7: Epiclon 153 brominated epoxy resin manufactured by Dainippon Ink Chemical Industry Co., Ltd. Epoxy resin equivalent: 400g/eq, n=0 Composition: 68%
环氧树脂8：大日本油墨化学工业公司制造Epiclon840S双酚A型环氧树脂环氧树脂当量：190g/eq，n＝0成分：86％Epoxy resin 8: Epiclon 840S bisphenol A type epoxy resin manufactured by Dainippon Ink Chemical Industry Co., Ltd. Epoxy resin equivalent: 190g/eq, n=0 Composition: 86%
环氧树脂9：大日本油墨化学工业公司制造Epiclon830S双酚F型环氧树脂环氧树脂当量：170g/eq，n＝0成分：78Epoxy resin 9: Epiclon 830S bisphenol F type epoxy resin manufactured by Dainippon Ink Chemical Industry Co., Ltd. Epoxy resin equivalent: 170g/eq, n=0 Components: 78
◆其它环氧树脂◆Other epoxy resins
环氧树脂10：壳牌化学公司制造EPON Resin 1031四官能型环氧树脂环氧树脂当量：212g/eqEpoxy resin 10: EPON Resin 1031 four-functional epoxy resin manufactured by Shell Chemical Company Epoxy resin equivalent: 212g/eq
环氧树脂11：东都化成制造TDCN-704甲酚清漆型环氧树脂环氧树脂当量：220g/eqEpoxy resin 11: TDCN-704 cresol varnish type epoxy resin manufactured by Tohto Kasei Epoxy resin equivalent: 220g/eq
◆固化剂◆Curing agent
固化剂1：日本环氧树脂公司制造YLH129B70双酚A型清漆二官能成分：17～19％羟基当量：118g/eqCuring agent 1: YLH129B70 bisphenol A type varnish manufactured by Japan Epoxy Resin Co., Ltd. Difunctional component: 17-19% Hydroxyl equivalent: 118g/eq
固化剂2：大日本油墨化学工业公司制造TD 2093酚清漆二官能成分：7～8％羟基当量：105g/eqCuring agent 2: TD 2093 phenolic novolac manufactured by Dainippon Ink Chemical Industry Co., Ltd. Difunctional component: 7-8% Hydroxyl equivalent: 105g/eq
固化剂3：大日本油墨化学工业公司制造VH-4170双酚A型清漆二官能成分：25％羟基当量：118g/eqCuring agent 3: VH-4170 bisphenol A type varnish manufactured by Dainippon Ink Chemical Industry Co., Ltd. Difunctional component: 25% Hydroxyl equivalent: 118g/eq
固化剂4：双氰胺试剂品理论活性氢当量：21g/eqCuring agent 4: Dicyandiamide reagent Theoretical active hydrogen equivalent: 21g/eq
◆催化剂◆Catalyst
催化剂1：四国化成公司制造：2-乙基-4-甲基咪唑Catalyst 1: Manufactured by Shikoku Chemicals Co., Ltd.: 2-Ethyl-4-methylimidazole
◆充填剂◆Filler
无机充填剂1：E玻璃粉Inorganic filler 1: E glass powder
无机充填剂2：硅石Inorganic filler 2: silica
无机充填剂3：滑石Inorganic filler 3: talc
◆有机溶剂◆Organic solvent
有机溶剂1：丁酮Organic solvent 1: Butanone
有机溶剂2：甲氧基丙醇Organic solvent 2: Methoxypropanol
有机溶剂3：环己酮Organic solvent 3: cyclohexanone
有机溶剂4：二甲替甲酰胺Organic solvent 4: Dimethylformamide
从表1可看出，实施例1～7与比较例1、比较例2、比较例3相比，可确保通用环氧树脂层叠板所必需的阻燃性及玻璃化转移温度，且具有良好的半固化片外观，其中，在比较例1中，未采用二官能环氧树脂b，该二官能环氧树脂通过使双酚A、双酚F及四溴双酚A中的任意一种与表氯醇进行反应而得到，且GPC图的n＝0成分为60％以上，在比较例2中，未采用溴化环氧树脂a，该溴化环氧树脂通过使双酚A型环氧树脂与四溴双酚A进行反应并混合而得到，环氧树脂当量为350g/eq以上470g/eq以下，且GPC图面积比的n＝0成分为20％以上35％以下，在比较例3中，未采用溴化环氧树脂a，该溴化环氧树脂通过使双酚A型环氧树脂与四溴双酚A进行反应并混合而得到，环氧树脂当量为350g/eq以上470g/eq以下，且GPC图面积比的n＝0成分为20％以上35％以下，而且，未采用二官能环氧树脂b，该二官能环氧树脂通过使双酚A、双酚F及四溴双酚A中的任意一种与表氯醇进行反应而得到，且GPC图的n＝0成分为60％以上。其中，实施例1～7采用溴化环氧树脂a，该溴化环氧树脂通过使双酚A型环氧树脂与四溴双酚A进行反应并混合而得到，环氧树脂当量为350g/eq以上470g/eq以下，且GPC图面积比的n＝0成分为20％以上35％以下，还采用一种以上的二官能环氧树脂b，该二官能环氧树脂通过使双酚A、双酚F及四溴双酚A中的任意一种与表氯醇进行反应而得到，且GPC图的n＝0成分为60％以上，且环氧树脂a与环氧树脂b的合计对环氧树脂整体而言为80重量％以上100重量％以下，最好为93重量％以上100重量％以下，环氧树脂a为75重量％以上97重量％以下，溴含有率对环氧树脂整体而言为18重量％以上30重量％以下。此外，与DICY固化系即比较例4相比，实施例1～7的热分解温度及烘箱耐热性等耐热性良好。As can be seen from Table 1, compared with Comparative Example 1, Comparative Example 2, and Comparative Example 3, Examples 1 to 7 can ensure the necessary flame retardancy and glass transition temperature of general-purpose epoxy resin laminates, and have good The appearance of the prepreg, wherein, in comparative example 1, did not use the bifunctional epoxy resin b, the bifunctional epoxy resin by making any one of bisphenol A, bisphenol F and tetrabromobisphenol A with epichlorine Alcohol is reacted and obtained, and the n=0 component of the GPC chart is more than 60%. In Comparative Example 2, brominated epoxy resin a is not used. The brominated epoxy resin is obtained by making bisphenol A type epoxy resin and Tetrabromobisphenol A is obtained by reacting and mixing, and the epoxy resin equivalent is more than 350 g/eq and less than 470 g/eq, and the n=0 component of the GPC chart area ratio is more than 20% and less than 35%. In Comparative Example 3, Brominated epoxy resin a is not used, and the brominated epoxy resin is obtained by reacting and mixing bisphenol A type epoxy resin with tetrabromobisphenol A, and the epoxy resin equivalent weight is more than 350g/eq and less than 470g/eq , and the n=0 component of the GPC figure area ratio is more than 20% and less than 35%, and the difunctional epoxy resin b is not used, and the difunctional epoxy resin is obtained by making bisphenol A, bisphenol F and tetrabromobisphenol Either one of A is obtained by reacting with epichlorohydrin, and the n=0 component of the GPC chart is 60% or more. Wherein, embodiment 1～7 adopts brominated epoxy resin a, and this brominated epoxy resin is obtained by making bisphenol A type epoxy resin and tetrabromobisphenol A react and mix, and epoxy resin equivalent is 350g/ More than eq and less than 470g/eq, and the n=0 component of the GPC figure area ratio is more than 20% and less than 35%, and more than one kind of difunctional epoxy resin b is also used, and the difunctional epoxy resin is made by making bisphenol A, Any one of bisphenol F and tetrabromobisphenol A reacts with epichlorohydrin, and the n=0 component of the GPC chart is 60% or more, and the total of epoxy resin a and epoxy resin b contributes to the ring The oxygen resin as a whole is 80% by weight to 100% by weight, preferably 93% by weight to 100% by weight, and the epoxy resin a is 75% by weight to 97% by weight. The bromine content is higher than that of the whole epoxy resin. In other words, it is not less than 18% by weight and not more than 30% by weight. Moreover, compared with Comparative Example 4 which is a DICY hardening system, Examples 1-7 were favorable in heat resistance, such as thermal decomposition temperature and oven heat resistance.
从成型性结果来看，采用了使酚清漆树脂，酚醛、甲酚、双酚A的任意一种与乙醛进行反应，而且官能成分为15％以上30％以下的清漆树脂的实施例1、2、4～7与未采用上述酚清漆的实施例3相比，成型性良好。From the moldability results, the phenol novolac resin, any one of phenol novolac, cresol, and bisphenol A reacted with acetaldehyde, and the functional component of the varnish resin was 15% to 30% in Example 1, 2. In 4 to 7, moldability is good compared with Example 3 in which the above-mentioned phenol novolac is not used.
从热膨胀率测定结果来看，与未添加无机充填剂的实施例1～4相比，采用了无机充填剂的实施例5、6、7的热膨胀系数较低。From the measurement results of thermal expansion coefficients, compared with Examples 1-4 without adding inorganic fillers, the thermal expansion coefficients of Examples 5, 6, and 7 using inorganic fillers are lower.
从玻璃化转移温度与热膨胀测定结果来看，采用了玻璃粉及硅石的实施例5、6不能降低玻璃化转移温度。From the measurement results of glass transition temperature and thermal expansion, the glass transition temperature cannot be lowered in Examples 5 and 6 using glass powder and silica.
Claims (6)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2003/007052 WO2004108791A1 (en) | 2003-06-03 | 2003-06-03 | Resin composition for printed wiring board, prepreg, and laminate obtained with the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1771274A true CN1771274A (en) | 2006-05-10 |
| CN100424110C CN100424110C (en) | 2008-10-08 |
Family
ID=33495915
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB038265303A Expired - Lifetime CN100424110C (en) | 2003-06-03 | 2003-06-03 | Resin composition for printed wiring board, prepreg, and laminate using prepreg |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US8470938B2 (en) |
| EP (1) | EP1637554B1 (en) |
| JP (1) | JP4915549B2 (en) |
| CN (1) | CN100424110C (en) |
| AU (1) | AU2003242007A1 (en) |
| TW (1) | TWI266790B (en) |
| WO (1) | WO2004108791A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104582278A (en) * | 2014-09-04 | 2015-04-29 | 陈鹏 | A kind of circuit board and preparation method thereof |
| CN110328914A (en) * | 2019-06-17 | 2019-10-15 | 吉安市宏瑞兴科技有限公司 | A kind of copper-clad plate and preparation method thereof suitable for PCB processing procedure with good flame-retardance |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070293614A1 (en) * | 2006-06-15 | 2007-12-20 | Zhou Wenjing J | Powder coating composition for pipe coating |
| KR100877342B1 (en) * | 2007-09-13 | 2009-01-07 | 삼성전기주식회사 | Flame retardant resin composition for printed circuit board, printed circuit board using same and method for manufacturing same |
| KR101091305B1 (en) | 2009-10-09 | 2011-12-07 | 유니플러스 일렉트로닉스 컴퍼니 리미티드 | How to prepare a sticky varnish with high thermal conductivity and low loss factor for stacking up additional insulation layers |
| EP2374828B1 (en) * | 2010-04-08 | 2016-07-20 | Nan-Ya Plastics Corporation | Preparation of a low dielectric brominated resin with a symmetric or saturated heterocyclic aliphatic molecular structure and composition comprising said resin |
| CN101892027B (en) * | 2010-07-08 | 2013-05-01 | 广东生益科技股份有限公司 | Low-halogen-content flame-retardant adhesive and flexible copper clad laminate prepared from same |
| CN102514304B (en) * | 2011-11-14 | 2014-08-27 | 上海南亚覆铜箔板有限公司 | Common Tg lead-free copper clad laminate and preparation method thereof |
| WO2014092019A1 (en) * | 2012-12-12 | 2014-06-19 | 株式会社ニコン | Composition, laminate, method for producing laminate, transistor, and method for producing transistor |
| US9526185B2 (en) * | 2014-04-08 | 2016-12-20 | Finisar Corporation | Hybrid PCB with multi-unreinforced laminate |
| US10647826B2 (en) | 2015-09-30 | 2020-05-12 | Nippon Steel Chemical & Material Co., Ltd. | Curable epoxy resin composition, and fiber-reinforced composite material obtained using same |
| CN110358252B (en) * | 2019-06-26 | 2021-07-13 | 建滔电子材料（江阴）有限公司 | Glue solution for producing lead-free high-reliability FR-4 copper-clad plate |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0768380B2 (en) * | 1992-04-24 | 1995-07-26 | 東芝ケミカル株式会社 | Prepreg for printed wiring board |
| JPH0748586B2 (en) * | 1992-04-24 | 1995-05-24 | 東芝ケミカル株式会社 | Method for manufacturing multilayer printed wiring board |
| JPH0812858A (en) * | 1994-06-28 | 1996-01-16 | Matsushita Electric Works Ltd | Epoxy resin composition, prepreg using the epoxy resin composition, and laminate board using the prepreg |
| JP2000154232A (en) * | 1998-11-20 | 2000-06-06 | Sumitomo Bakelite Co Ltd | Heat-resistant resin composition, and prepreg and laminate using same |
| US6558797B1 (en) * | 1998-12-22 | 2003-05-06 | Hitachi Chemical Company, Ltd. | Adhesive-coated copper foil, and copper-clad laminate and printed circuit board both obtained with the same |
| GB2362037A (en) * | 2000-05-03 | 2001-11-07 | Bancha Ongkosit | Printed circuit board manufacture |
-
2003
- 2003-06-03 AU AU2003242007A patent/AU2003242007A1/en not_active Abandoned
- 2003-06-03 EP EP03733281.4A patent/EP1637554B1/en not_active Expired - Lifetime
- 2003-06-03 WO PCT/JP2003/007052 patent/WO2004108791A1/en not_active Ceased
- 2003-06-03 JP JP2005500537A patent/JP4915549B2/en not_active Expired - Lifetime
- 2003-06-03 US US10/559,556 patent/US8470938B2/en not_active Expired - Lifetime
- 2003-06-03 CN CNB038265303A patent/CN100424110C/en not_active Expired - Lifetime
-
2004
- 2004-03-23 TW TW093107844A patent/TWI266790B/en not_active IP Right Cessation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104582278A (en) * | 2014-09-04 | 2015-04-29 | 陈鹏 | A kind of circuit board and preparation method thereof |
| CN104582278B (en) * | 2014-09-04 | 2017-08-29 | 陈鹏 | A kind of circuit board and preparation method thereof |
| CN110328914A (en) * | 2019-06-17 | 2019-10-15 | 吉安市宏瑞兴科技有限公司 | A kind of copper-clad plate and preparation method thereof suitable for PCB processing procedure with good flame-retardance |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2004108791A1 (en) | 2006-07-20 |
| TW200500413A (en) | 2005-01-01 |
| EP1637554B1 (en) | 2015-07-29 |
| AU2003242007A1 (en) | 2005-01-04 |
| CN100424110C (en) | 2008-10-08 |
| EP1637554A4 (en) | 2011-08-24 |
| JP4915549B2 (en) | 2012-04-11 |
| US20060159928A1 (en) | 2006-07-20 |
| US8470938B2 (en) | 2013-06-25 |
| EP1637554A1 (en) | 2006-03-22 |
| WO2004108791A1 (en) | 2004-12-16 |
| TWI266790B (en) | 2006-11-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1717451A (en) | Hardener composition for epoxy resins | |
| CN1293147C (en) | Thermosetting resin composition and prepreg and laminated sheet using the same | |
| CN1219822C (en) | Thermosetting resin composition and prepreg laminate for circuit board and printed circuit board each made therewith | |
| CN100341938C (en) | Halogen-free nonflammable epoxy resin composition, halogen-free nonfammable epoxy resin composition for build-up type multi-layer board | |
| CN1206279C (en) | Thermosetting polyphenylene ether resin composition, cured resin composition obtained therefrom, and lamiated structure | |
| CN1130427C (en) | Epoxy resin composition and semi-solidified sheet and multilayer printed circuit board produced therewith | |
| CN1390246A (en) | Flame-retardant epoxy resin composition and liminate made with same | |
| CN1803916A (en) | Resin composite and prepreg and laminate materials used thereof | |
| CN1060771C (en) | Aryl ester compound and its preparation method, epoxy resin composition using the compound and its copper-clad laminate | |
| CN1826365A (en) | Resin composites for printed circuit boards, prepregs, laminates and printed circuit boards produced therefrom | |
| CN1239609C (en) | Resin compositions, uses thereof, and methods for their manufacture | |
| CN1788053A (en) | Flame-retarded epoxy resin composition, prepregs containing the same, laminated sheets and printed wiring boards | |
| CN1771274A (en) | Resin composition for printed wiring board, prepreg, and laminate obtained with the same | |
| CN1317329C (en) | Resin composition, prepreg and laminate using the composition | |
| CN101044204A (en) | Non-halogen flame retardant epoxy resin composition, and prepreg and copper-clad laminate using the same | |
| CN1212354C (en) | Fire-retardant resin composition, preliminary-dip piece, laminated board, metal cladded laminated board, printed circuit-board and multi-layer printed circuit board | |
| CN1239615C (en) | Curable resin composition | |
| CN1106273C (en) | Phenol-novolacs with improved optical properties | |
| CN1289600C (en) | Thermosetting epoxy resin composition and its formed body and multilayered printed circuit board | |
| JP4317380B2 (en) | Modified polyimide resin composition and prepreg and laminate using the same | |
| CN1050730A (en) | Polyphenylene ether-composite epoxy resin systems for laminated circuit boards | |
| CN1639223A (en) | Phosphorus-containing epoxy resin, phosphorus-containing epoxy resin composition, process for producing the same, and sealing material and laminate board | |
| JP5040102B2 (en) | Prepreg and laminate | |
| CN1249128C (en) | Flame Retardant Resin Composition | |
| JP4198508B2 (en) | Modified polyimide resin composition and prepreg and laminate using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20081008 |